Triazine derivatives



butylphenyl,

Patented Nov. 23, 1943 Pittsfleld, Mass., 'assignors to General Company,a corporation of New York Application Ma as, 1942. Serial No. 444,264

No Drawin Electric 26 Claims. (or. 260-248) This invention relates tonew chemical compounds and more particularly to triazine derivatives.The invention especially is concerned with the production of new anduseful diamlno triazinyl halogeno carboxy-, carboaliphaticoxyandcarboaromaticoxy-alkyl sulfides.

The chemical compounds of this invention may be represented by thefollowing general formula:

NHR

In the above formula n represents an integerand is'atleast 1 and notinore than 2, X represents a halogen atom, more particularly a chlorine,

compounds such, for instance, as those reprebromine, fluorine or iodineatom, and It represents a member of the class consisting of hydrogen andmonovalent hydrocarbon and substituted hydrocarbon radicals, moreparticularly halo-hydrocarbon radicals. I

Illustrative examples of radicals that R in the above formula mayrepresent are: aliphatic (e. g., methyl, ethyl, propyl, isopropyl,butyLsecondaIY butyl, isobutyl, butenyl, amyl, iso'amyl, hexyl,

'octyl, allyl, methallyl, ethallyl, crotyl, etc), in-

cluding cycloaliphatic (e. g., cyclopentyl, cyclopentenyl, cyclohexyl,cyclchexenyl, cycloheptyl, eta); aryl (e. g., phenyl, diphenyl or xenyl,naphthyl, etc.); aliphatic-substituted aryl (e. g., tolyl, xylyl,ethylphenyl, propylphenyl, isopr opylphenyl, allylphenyl,2-butenylphenyl, tertiaryetc.) aryl-substituted aliphatic (e. g,.benzyl, phenylethyl, cinnamyl, phenylpropyl, etc.); and theirhomologues, as well as those groups with one or more of their hydrogenatoms substituted by, for example, a halogen, more particularlychlorine, bromine, fluorine or iodine. Specific examples ofhalogeno-substituted hydrocarbon radicals are chloromethyl, chloroethyl,

chlorophenyl, dichlcrophenyl, chlorocyclohexyl,

ethyl chlorophenyl, phenyl chloroethyl, bromoethyl, bromopropyl,fluorophenyl, bromotolyl, etc. Preferably R in the .--NHR roupings ofFormula I is hydrogen and the R inthe GOOR grouping is either hydrogenor an unsubstituted monovalent hydrocarbon radical, e. g., an aliphaticradical such as methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl,methallyl, crotyl, etc. However, there also may be produced iiiaccordance with-the present invention iodophenyl,

sented by the general formulas:

. NHR

n arm-E c-s[ c.m.-ar)cooap and, more particularly.

v r N/ n I11 BIN-E t-s-i(o.m.-ici -cooaq and .mNJ IKe-s uomi isn oaqwhere n, X and Rhave the same meanings as given above with respect toFormula I and R (Formulas III and IV) represents hydrogen'or anunsubstituted hydrocarbon radical, numerous ex-' amples of which havebeen given above.

The new-compounds of this invention may be.

used, for example, as pharmaceuticals, plasticizers and as intermediatesin the preparation-oi derivatives thereof such-as hydrazo, hydrazine,carbazido, semicarbazido, ureido, amidine, methylol,

etc., derivatives of the individual compound embraced by Formula 1.Compounds containing a COOH grouping may be amidated; or the drogen ofthe carboxy grouping may b replaced by a substituentsuch, for instance,a an ammonium radical or a monovalent metal, e. g., an

alkali metal such as sodium, potassium, lithium,

etc. Our new compounds are especially valuable in the preparation ofsynthetic resinous composi-. tions. Thus, they may be condensed with,for instance, aldehydes, including polymeric aldehydes, hydroxyaldehydeand aldehyde-addition products, to yield condensation products ofparticular utility in the plastics-and coating arts.

They are particularly useful as such or in the form of their soluble,fusible aldehyde-reaction products as agents for accelerating theconversion of acid-curing thermosetting resins, e. g., acidcuringthcrmosetting aminoplasts and phenoplasts, to an insoluble, infu'siblestate. (In our copending application Serial No. 444,263, tiled May 23,1942, and assigned to the same assignee as the present invention, wehave more fully described and specifically claimed compositionscomprising the product of reaction of ingredients comprising an aldehydeand a compound of the kind represented by Formula I; and compositionscomprising an acid-curing, thermosetting resin carrying a curing agenttherefor comprising a compound-of the kind represented by Formula I or asoluble, fusible aldehyde-reaction product of such a compound.) Thes newcompounds also may be compounded with rubber, both natural andsynthetic, to modify th properties of the rubber. 4

Various methods may be. employed to produce the chemical compounds orthis invention. We

prefer to prepare them by effecting reaction, in the presence of ahydrohalide acceptor, between equimolecular proportions of a mercapto(mono- -'n'iercapto) diamino s-triazine (symmetrical triazine) and ac'orboxy-, carboaliphaticoxyor carboaromaticoxy-alkyl dihalide. When acarboxy (-COOH) alkyl dihalide is used as a starting reactant and theproportions of reactants and reaction conditions are such that thehydrogen atom or the -COOH grouping is replaced by the residue of thehydrohalide acceptor, e.'g., by an alkali metal, the carboxy compounddesired as a final product is obtained by treating this intermediateproduct wth hydrochloric, hydrobromic, sulfuric or other suitableinorganic or organic acid in an amount just suflicient to torm thedesired carboxy derivative.

, Illustrative examples or diamlno mercapto s-triazines that may beemployed, depending upon the particular end-product. sought, are:

2-mercapto 4,6-diamlno s-triazine (4-mercapto 2,6-diamino aminos-triazine) 2-mercapto afi-di-(methylamino) s-triazine z-mercapto4,6-di-(anilino) s-triazlne 2-mercapto 4-amino fi-ethylamino s-triazinez-mercapto 4,6-di-(propylamino) s-triazine s-triazine; 6-mercapto,2,4-,di-,

'2-mercapto 4-allylamino B-butylamino s-triazine z-mercapto4-isobutylamino fi-cyclopentylamino s-triazine 2-mercapto4-(3-butenylamino) 'g mino s-triazine 2-mercapto 4-pentylaminofi-cyclohexylamino' s-triazine 2-mercapt'o 4-hexylamino fi-xenylaminos-triazine Y Z-mercapto 4-cyclohexenylamino fi-naphthylamino s-triazinez-mercapto 4-chlorocyclopentylamino 6-toluido s-triazine 2-mercapto4-bromotoluido 6-benzylamino s-triazine '2-mercapto4-phenylchloroethylamino' (i -phenethylamino s-triazine 2-mercapto4-chloroanilino B-ethylphenylamin s-triazine Z-mercapto4-cycloheptylamino 6-isopropylphenylamino s-triazine 2-mercapto4-propylanilino B-phenylpropylamino s-triazine I 2-mercapto4-dich1oroanilino 6-ch1oroethylamino s-triazine 2-me'rcapto 4,6-di-(fluoroanilino) s-trlazine z-mercapto 4,6-di-(bromotoluido)'s-triazine Z-mercapto 4,6-di4iodoanilino) s-triazine z-mercapto a-aminofi-bromoethylamino s-triazine Z-mercapto 4- amino 6-methylaminos-triazine 2-mercapto 4-amino fi-ethylamino s-triazine Z-mercaptoa-amino 6-benzylamino s-triazine i The dichloro carboalkoxy (e.

2-mercapto 4-amino G-xenylamino s-triazine 2-mercapto GaminoG-propylanilno s-triazlne 2-mercapto 4-amino o-chloroethyl mino s-triazine 2-mercapto 4-amino S-na'phthylamino s-trlazine 2-mercapto4,6-di-(cyclopentylamino) s-triazine z-mercapto 4-isobutylaminofi-neopentylamino s-triazine 2-mercapto 4-benzylamino fi-toluidos-triazine Z-mercapto 4-cyclohexylamino 6-xylidino s-trlazine2-rnercapto 4-phenethylamino 6-ohloropropylamino s-triazine Illustrativeexamples of carboxy-, carboaliphaticoxyand carboaromaticoxy-alkyl'dihalides that may be used, depending upon the desired end-product, are:

Beta,beta-dich.loro carboethoxy ethane Beta,beta-dibromo carboethoxyethane Beta',beta-dich1oro carbopropoxy ethane Beta,beta'-dibromocarbopropoxy ethane Alpha,alpha-dichloro carbopropoxy ethaneAlpha-alpha-dibromo carbopropoxy ethane Alpha,beta-dichloro carbopropoxyethane Alpha,beta-dibromo earbopropoxy ethane Alpha,alpha-diiodocarboethoxy ethane Alpha,alpha-diiodo carbophenoxy propane Alpha-bromoalpha-iodo gamma-phenyl carbonaphthoxy propane Beta,beta-dichlorocarbotoloxy ethane Be'ta-isobutyl beta,beta-dibromo carbo-xyloxy ethaneA Alpha-chlorophenyl beta-naphthyl beta,beta-diiodo carbobenzoxy ethaneAlpha-'cyclopentyl alpha-tolyi beta-chloro betaiodo carbophenethoxypropane Alpha-benzyl beta-cyclohexyl alpha,beta-dichlorocarbocyclopentoxy pentane Alpha-xylyl beta,beta-diphenyl alpha,beta-di'-bromo carbocyclohexoxy ethane Alpha-bromonaphthyl alpha,beta-dichlorocarbophenoxy ethane Beta-phenyl alpha,beta-dichloro carboetlwxy propaneBeta-ethyl P pane Various hydrohalide acceptors may be employed. Wepreferto use a hydrohalide acceptor that will react with the mercaptotriazlne to form a water-soluble salt.' Examples of such ac-' ceptorsare the alkaiil-metal' hydroxides, e. z.. sodium hydroxide, potassiumhydroxide, etc. Additional examples of hydrohalide acceptors thatalpha,beta -dibromo carbophenoxy beta-cresyl beta-tolyl may be used areother inorganic bases. e. g., calclum hydroxide, barium hydroxide,ammonium hydroxide, etc.; carbonates of inorganic bases,

including the carbonates of alkali metals: organic amines such astertiary amines, e. g., trimethyl amine, triethyl amine, tributbylamine,

pyridine, dimethyl aniline, quinoline, etc.: qua-, ternary ammoniumbases, e. g., tetramethyl ammonium hydroxide, etc.; and the like.

The reaction between the mercapto diamino sasaaoss Alpha, beta-dichlorotriazine and the chosen carboxy-, carboallphatl- I coxyorcarboaromaticoxy-alkyl dihalide may be carried out in any suitablemanner, but preferably is effected in the presence of a suitable solventor mixture of solvents. Although various solvents and solvent mixturesmay be employed, for economic reasons and because of their eminentsuitability we prefer to use water or a mixture of water and alcohol.The reaction may becarried out under a variety or temperature andpressure conditions, for instance at normal-labnormal or at elevatedtemperatures and at atmospheric, sub-atmospheric or super-atmosphericpressures.

The above reaction may be represented by the following general equation:

hydrohallde acceptor -Ra--1X:)C00R --o g NHR t ha s 33th.! man-d)z-s-Kcmhm-coom y a acceptor In the above equation 1:, R and x have thesame meanings as given above with reference to Formula I.

The new chemical compounds of this invention also may be prepared by aprocess which coinprises efiectingreaction between approximatelyequimolecular proportions of a halogenated diamino s-triazine and acarbniw, carboalophatioxy .or carboaromaticoxy monomercapto monohalide.This reaction preferably is carried out in the presence of an anhydroussolvent. An an- Parts 2 8.5

Thioammeline carbomethoxy ethane Sodium hydr Water 350.0

were stirred rapidly together at room temperature for 17 hours, yieldinga solid precipitate comprising diamino s-triazinyl chlorocarbomethoxy-ethyl sulfide. This precipitate was removed by filtration,washed free of soluble salts and dried to obtain the purified product.

- Example 2 This example illustrates the preparation of diaminos-triazinyl bromo carbomethoxy-ethyl sulfide.

Parts Thioammeline -L 28.5

,Sodium hydroxide Water Alpha, beta-dibromo carbomethoxy ethane 49.2

350.0 were stirred together rapidly at room tempera:

ture for 16 /2 hours, yielding a solid precipitate comprising diaminos-triazinyl bromo carbomethoxy-ethyl sulfide. This precipitate wasfiltered oil, washed tree of soluble salts and dried at'room temperatureto obtain the purified product.

Emmpled 4,6-di-(methylamino) s-triazinyl-2-chloro carbomethoxy-ethylsulfide is produced in essentially the same manner as described underExample l with the exceptionthat, instead of thioammeline, an equivalentamount of z-mercapto 4.6-di-(methylamino) s-triazine is employed.

7 Example 4 .Diam'ino s-triazinyl chloro carboethoxy-ethyl sulfide isprepared in essentially the same manhydrous solvent, e., g., alcohol, isdesirable because one of thereactants, namely, the halogenated diaminos-triazine, is hydrolyzable. The other conditions for preparing thecompounds of the invention may be the same as described above withreference to the first-mentioned method, of

preparation.

In order that those skilled in the art better may understand how thepresent invention may be carried into eflect, the following illustrativeexamples are given. All parts are by weight.

Example 1 This example illustrates the preparation of diaminos-trlazinyl chloro carbomethoxy-ethyl sulfide, the formula for which isN where n has a value of 2.

ner as described under'Example 1 with the exception that, instead ofalpha, beta-dichloro car- I bomethoxy ethane, an equivalent amount ofalpha, beta-dichloro carboethoxy etlnne is employed.

Example 5 Diamino s-triazinyl chloro carbophenoxy-ethyl sulfide isproduced in essentially the same manner as described under Example 1with the exception that, instead of alpha,beta-dlchloro carbomethoxyethane, an equivalent amount of alpha,beta-dichloro carbophenoxy ethaneis used.

Other examples of the chemical compounds of this invention are listedbelow:

s-triaainyl .fiuoro carboaroxy-methyl sulfides 4-amino B-methylamino4,6-di- (cyclopentylamino) The diamino s-triazinyl halogeno (chloro,bromo,

ido, fiuoro) carboaliphaticoxy (e. g., carboalkoxy) -ethyl sulfides Thediamlno s-triazinyl halogeno (chloro, bromo,

iodo, fluoro) carboaroxy (e. g., carbophenoxy;

carbotoloxy, etc.)-ethyl sulfides The diamino s-triazinyl halogeno(chloro, bromo, iodo, fiuoro) carboxy-ethyl sulfides s-triazinyl-2 chlorcarboxy-methyl sulfide 4,6-di-(ethylamino) s-triazinyl-2- bromocarboxy-methyl sulfide 4,6-di-(anilino) s-triazinyl-2 cl'ilorocarboxymethyl sulfide 4,6-di-(bromoanilino) s-triazinyl-2 bromocarboxy-methyl sulfide 4,6-di-(cyclohexy1amino) carboxy-methyl sulfides-triazinyl-2 chloro 4,6-diamino s-triazinyl-Z 'alpha-(alpha-chloro Ycarbomethoxy-ethyl) sulfide 4,6-diamino s-triazinyl-2 beta (beta bromo'carboethoxy-ethyl) sulfide 4,6-diamino s-triazinyl-Z alpha- (betachloro4,6-diamino s-triazinyl-2 beta-(alpha-bromo carbophenoxy-ethyl) sulfide4,6-diamino s-triazinyl-Z alpha-(alpha-chloro carbophenoxy-propyl)sulfide 4,6-di-(anilin) s-triazinyl-2 alpha-(alpha-iodocarbophenoxy-propyl) sulfide s-triazinyl-2 alpha- (gamm -phenyl alpha-chloro carbonaphthoxy-gropyl) sulfide 4-ethylamino -6-aminos-triazinyl-2 beta-(betachloro carbotoloxy-ethyl) sulfide4-isobutylamino 6-neopenty1amino s-triazinyl-Z beta-(alpha-phenylbeta-naphthyl beta-iodo carbobenzoxy-ethyl) sulfide 4-naphthylaminoG-amino s-triazinyl-Z beta- (beta-isobutyl beta-bromocarbo-xyloxy-ethyl') sulfide 4-benzylamino 6-toluido s-triazinyl-2 beta-(alpha-tolyl al'pha-cyclopentyl betachloro carbophenethoxy-propyl)sulfide 4-phenethylamino fi-xylidino s'-triazinyl-2alpha-(alpha-phenethyl beta-phenyl beta-bromo carbocyclopentoxy-ethyl)sulfide 4,6-diamino s-triazinyl-2 alpha-(alpha-chloro carboxy-ethyl)sulfide 4,6-diamino s-triazinyl-2 bet'a-(beta-bromo carboxy-ethyl)sulfide 4,6-diamino s-triazinyl-2 alpha-(beta-chloro carboxy-ethyl)sulfide boaliphaticoxyand carboaromatic-oxy-methyl similar compounds maybe prepared in which two or three sulfur atoms are attached directly toa carbon atom of the triazine nucleus and which have attached to eachsulfur atom a grouping, wherein n, X and R have the same I meanings asgiven above with reference to Formula I.

What we claim as new and desire to secure by Letters Patent of theUnited States is:

1. Chemical compounds corresponding to the general formula where nrepresents an integer and is at least 1 and not more than 2, Xrepresents a halogen atom, and R represents a member of the classconsisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbonradicals.

2. Chemical compounds as in claim 1 wherein' R represents a hydrogenatom.

3. Chemical compounds as in claim 1 wherein- X represents a chlorineatom.

4. Chemical compounds as in claim 1 wherein x represents a bromine atom.v

5. Chemical compounds "corresponding to the general formula 4,6-diaminos-triazinyl-2 beta (alpha 7 bromo carboxyl-ethyl) sulfide4-cyclopentenylamino 6-xylidino s-triazinyl-z beta-(alpha-chlorobeta-benzyl carboethoxy-- 4-amino G-methylamino s-triazinyl-2 alpha-(beta-chlorophenyl beta-chloro carboethoxyethylisulfide In a mannersimilar to that described above I NHR N I Himo-s-uoma-lcn-mooa'l \Nwhere n represents an integer and is at least 1 'and not more than 2,and R. represents a-member ofthe class consisting'of hydrogen'andunsubstituted monovalent hydrocarbon radicals.

7. Chemical compounds corresponding to the general formula where nrepresentsan integer and is at least 1 and not more than 2, and 3'represents a memher or the class consisting of hydrogen andunsubstituted monovalent hydrocarbon radicals.

A a. a diamino s-triaz'inyl halogeno carboaliphaticoxy-ethyl sulfide. V9. A diamino s-triazinyl chlorocarboalkoxy ethyl sulfide. 1

10. A diamino s-triazinyl chloro carbomethoxy- 11. A diamino s-triazinylbromo carboalkoiw- 12. A diamino s-triazinyl bromo carbomethoxy- 13. Adiamino s-triazinyl maticoxy-ethyl sulfide.

14. A diamino s-triazinyl chloro carboaromaticoxy-ethyl sulfide.

' 15. A diamino s-triazinyl chloro carbophenoxyethyl sulfide.

16. The method of preparing chemical compounds corresponding to thegeneral tormula haiogeno carboarowhere n represents an integer and atleast 1 and not more than 2, x represents a halogen atom, and Rrepresents a member of the class consisting of hydrogen and monovalenthydrocarbon and halo-hydrocarbon radicals, said method comprisingeflecting reaction, in the presence of ahydrohalide acceptor, betweenapproximately q i olecular proportions of (l) a mercapto triazinecorresponding to the general formula NEE where R has the meaning abovegiven, and .(2) ,a compound corresponding to the general formula(CaRin-IXI) -COOR where n, X and B have the meanings above given.

17.. A method as in claim 16 wherein X represents a chlorine atom andthe hydrohalide acceptor is an alkali-metal hydroxide.

18. A method as in claim 16 wherein X represents a bromine atom and thehydrohalide acceptor is an alkali-metal hydroxide.

19. The method or preparing diamino s-tri- "azinyl chiorocarbomethoxy-ethyl sulfide which comprises eflecting reaction, in thepresence oi! a hydrohalide acceptor, between approximately equimolecularproportions of thioammeline and ammo F. n'smmo. JAMES -w. UNDERWOOD.

cums-1cm: or com-anon, I Patent arm-2,555,015. Iovenber 25, 1915 ammo F.nmjmumm' AL.

it ishereby certified that error .dppe ars' in the printed specificationof-the abbve minbe'red patent requiring correction as follows: Page 1,first Qtoflumn, line 15, before the formula insert the Roman numeral--I--; 13 3 "first column, line 20, for "cort ox yread -a csrboxyline.57, after read. itributyl line 21, for "norme.l-su b" reed normal, su-j-' "(r-mercypto' strike ont'the comma; and seeonql column, line Ii-1,5,- for "carboaliphatice'xy-" reed carboelipheticoxr lines 37 M15,for'Alphlalpha-F. .reed A'lphemlphspage 3 first column iine 6, for'tributbyl" line 1 .9-50 for "carboaiophatioxy" reed --esrboa1iihaticoxy-; line 72, a before the formula insert the Roman numeral-VI---; page 1;, first column,

line 1 for Fido read --iodo--; line 67, for "carboxyl' read carboxy--;

. and second column, line 3, for *cerbos romatic-oxy-xgethyl' reed-.-cerb0arometicoxy-methyland that the said Letters Patent shlouldieread with this correction therein that the sane may conform to therecord of me us in" the Patent Office.

Signed and sealed this 25th day 1' January, A. 1). 191m.

Henry Van Arsdale,

(Seal) Acting Commissioner of Patents.

